Method of making stannic chlorid.



PATENTED JAN. 21; 1908.

E. .A. SPERRY. METHOD OF MAKING STANNIO GHLORID.

APPLICATION F ILED MAR. 5 1906.

4 SHEETS-SHBET 1.

No. 877,247. PATENTED JAIL 21', 1908.

I E. A. SPERRY. METHOD OF MAKING ETANNIC OHLORID.

APPLICATION FILED MAR. 5, 1906.

4 SHEETS-SHEET 2.

IIIIH (5W E M 1 B. A. SPERRY. H METHOD OF MAKING STA NNIG OHLORID.

APPLIOATION FILED MAR. 5, 1906.

PATENTED JAN. 21, 1908.

' 4 SHEETS-SHEET 3.

[/VVE/VTOR Nor877,247. PATENTED JAN. 21, 1 908.?

' B. A. SPERR'Y. METHOD OF MAKING'STANNIG GHLORID.

APPLICATION FILED MAB. 6, 1906.

' 4 SHEETS-SHEET 4.

@ f9 )7 ifyli I f/VVE/VTOR M! By K Fig. is u sidc which may be construc lead, or which may be constructed cl" or lined UNT 'srirr. ABET rrc.

ELMER ll. SPERRY, OF BROOKLYN,

COMPANY, OF NEW YORK, N.

NEW YORK, ASSIGNOR TO CHEMICAL REDUCTlON Y., A CORPORATION OF NEW YORK.

METHOD OF MAKING STANNIC CHLORID.

Specification of Letters Patent.

Patented Jan. 21, 1908.

Application filed March 5 1906. Serial No. 30L3Z3.

of New York, have invented certain new and useful Improvements in Methods of Making Stannic Chlorild, of which the following is a specification. l

This invention is a. method of making 'stannic chlorid by reactidn between chlorin and metallic tin or a body containing the same.

According to my invention amaterial consisting Wholly or in part of metallic tin, hereinafter referredto as tin-bearing material, is brought into, contact with liquid stannic chlor'id and preferably maintained in suspension therein, said liquid sta nnic chlorid being exposed to contact with chlorin under conditions lavorz bleto the absorption of the gas. The stannic chlorid is preferably circulated in contact with the (ZlllOllll; p 1 rtions of the same mziy be cxposwl. as films to the gas; and those portions at which the absorption occurs are preferably mantained at a lower temperature than the region of reaction. for the purpose oi promoting the absorption. For this purpose. i may provide divided but minmninicziling bodies oi -stannic chlorid, which may be locnted in a single re.- action vessel, and to eii'cct a rapid interchange oi liquid between said bodies.

For n. lull understliruiing oi my invention reference is made to the accompanying draw--- ings, wherein;

Figure l is a control longitudina section of a form of reaction for ryi my nmthod into eil'ect 2 is a. horimntzil sec tion oi the same on a somewhat filllltllfii' scale on line 2*? of Fig. l the septum and reciprocating devices being rumor ed; l elevation on the same smile as parts" bein broken an h and the srptuin and (llSlin". 3 is a side I l. l l l l g l l l l l l l l l l rcciy'n'ocaiing devices removed; Fig. 4 is a.

detail seriion of one ol the connections; elmfz'iiion oi plant for the production oi" stunnic chlorid, in nccordainxc with my process; Fig. 5 is a plan View of the same; Fig. 'i is n vrrticol transwrsc ieclion oi' the still; and l igg. H is a dizigran'nnntic 'v'lQE. ill usirnling the nrrangys-mont of lilting blades in the still.

1 represents a relative-l d oi shallow vessel cast-iron or l l l l l l l ll l body of the vessel is provided with a jacket 2 having tangential inlets 3, 3 for steam or Water, and an outlet 4, this arrangement being found to insure a substantially even heating or cooling effect. The cover 5 is ren1ovhave observed that able, and is provided with interior passages 6 for a temperature controlling medium. The cover supports a removable hopper 7 jacketed as shown at 8 for heating the contents thereof; the hopper is provided with a cover 9 and depends into the vessel as shown at 10 to a suliicient depth to be sealed by the liquid therein. Charging means 1]. the hopper are preferably provided with means, indicated at 12, for heating themcoming material.

13 a septum, suitably supported Within the vessel, and illustrated as a horizontal ring-shaped disk, spaced from the walls of the vessel at its periphery and having, a central aperture 14. A hollow shaft 15 extends througha stulling-box 1.6 in the c ver and carries t its l wer end arms 17 supporting an annular disk 18 to which are secured lifting and stirring blades 19. These blades preferably two in number and are oppositely disposed, the eilect of this arrangement, together with the conformation of the blades, beingto produce a Wave action at the surface of the liquid, the purpose-of which is to expose an extended surl'zwe of the same as hcre inatter more fully explained. The blades extend approximately to the bottom of the vessel and are lorwnrilly inclined in the directioi'i of movement in such manner to exert a li ting action on its liquid or solid contents; the outer ondsol' the blades may be curved backward as shown, the (losign being such as to insure on equal distribution of the muterials with which they come in roniect. The blades serve t import to the liquid contents oi the vessel a movement of circulation which in the particular form of device illust nit-d is outward beneath the disk l3 and inward above the same. by the shalt l5 and rotate thcrcwith'il del preferably mount agitating devices, tl\c purpose of which to maintain iinelydivided solid matter in. suspension in the circulating liquid,

The d isk 13 may be carried located above l lll to the and to agitate it violently in-contact there with. As one form of agitating device I have shown inclined blades mounted near the bottom of the vessel and adapted to the curvature of the same, carried by a shaft 21 supported in a bearing in a lug 22 on the disk 18. A gear 23 secured to the blades 20.

perforated disk 26 and to provide means for reciprocatin the same in a vertical direction, the means s own comprising a'plurality of rods 27 of which one only is shown, secured disk 26 and extending through stuffing boxes 28 in the cover downward movement is imparted to the disk by a lever 29 actuated by a cam 30 on the shaft 15 a spring 31 serves to return the disk to its upper position. The disk 26 serves to maintain the solids in suspension in the portion of the liquid above the septum 13, and further serves to support a plurality of strips or pieces of wire-gauze or equivalent fabric or suitable structure 32, the function of which is to lift the liquid above its normal level and to expose extended surfaces of the same to'the action of the gas in the upper portion of the vessel. actor and material of the liquid-exposing devices 32 will .depend upon the materials treated; they should be substantially unattacked by the gas or the solvent liquid, and should possess such structure as to be capable of retaining a film of the liquid, thereby exposing both surfaces thereof for absorption of the gas. Perforated sheets or fabrics,

: whether metallic or otherwise, may be available for this purpose, or any device which will carry the liquid into the gas space will fulfil this function.

In order to improve the intimacy of contact between gas and liquid I prefer to direct the former in a restricted path above the latter, and for this purpose I provide battles or depending partitions 33 extending transversely across the vessel and adapted to be sealed by the liquid therein. The arrangement of the baffles is such as to direct the gas in a tortuous path between the inlet and outlet 46, 47. In addition to their function in directing the gas the partitions 33 cooperate with the circulating blades 19, in that they are in position to bewetted by the waves produced by these blades, thus exposing a constantly renewed liquid 'lilnror surface to the gas; during the reaction period stanmc ChlUI'Hl eomlenses on the under surface of the The char-.

upper end of the discharge conduit 35; the

latter is illustrated as of special construction, comprising an angular cross 36 of which the lower aperture carries a stuffing box 37 for the valve stem 38, while one of the lateral apertures carries a removable plug 39 for convenience in cleaning. The stem 38 may be reciprocated through the stuffing-box for operating the valve, and carries at its lower end a handle 40 by means of which the valve may be rotated for the pur ose of grinding it to its seat or for clearing it om matter which would interfere with its seating. This feature is of particular value in valves forthe discharge of finely divided solid matters.

In Fig. 4 I have shown in detail a preferred form of gas connection, comprising a' pipe 41 having an upwardly inclined outer end 42, a removable closure 43 therefor, and

a branch pipe 44 for the gas. The purpose of the upward inclination of the ends 15 to permit inspection or cleaning of the pipe 41 without danger of loss of the liquid contents of the vessel. At 45 I have shown a heat-insulating covering which is applied 'to the gas outlet pipe and which serves to prevent 'condensation or separation therein of any vola A tile reaction products; by pro erly covering said pipe I find that I am enab ed to substantially prevent clogging of the same, as, for instance, by the separation of hydrated, stannic chlorid in the production of stannic chlorid as hereinafter referred to. The liquid outlet in a vessel provided with circulating and agitating means may be substantially similar in construction, except that a downward turned branch pipe is provided; such outlet may be located somewhat above the normal liquid level, the wave action above referred to" being sufficient for the discharge of any accumulation of ii uid.

In most cases it is desirable t at the asabsorbihg surfaces of the liquid shoul be maintained at a lower temperature than the reaction zone where the absorbed gas is brought into contact with the solid matter, it being well understood that absorption or solution of the as ismore rapid at lower temperatures. n the present construction this is provided for by means of the watercooled cover t-hrou h which heat is abstracted not only from t e gas chamber itself but from the partitions 33, which SBIKG asabove pointed out as sup )lemental surfaces for the exposure of films of liquid. By means of the jacket 2 such temperature is maintained in the region of reaction as is most favorable under the particular conditions.

Referring to Figs. 5-8 I have shown the general arrangement of a plant comprising two reaction vessels 1, 1 arranged to dischlorid, thl subsequent charge through their outlets 35 into a still 48 capes, together with any associated .or env trained stannic chlorid, to the condensers 49. It is in part condensed therein and the liquid chlorid is permitted to flow back into the reaction vessel through pipes 50. overflow for the chlorid, which may, as above stated, be somewhat above the normal liquid level, the stannic chlorid, together with some tin-bearing material or residue in suspension, being discharged through pipe 51 into a re.- ceptacle 52, from which it may be trans ferred to the still 48. The effect of the return-flow 50 and the overflow 51- is to maintain a substantially constant volume of material in the reaction vessel throughout the operation. When the reaction is complete the valve 34 is lifted to discharge the con-- tents of the vessel into the still. Any chlorid which passes through the condensers 49" is permitted to pass through conduit 53 to a suitable scrubber in which it is absorbed by water or other solvent.

The chlorin rmy in practice contain considerable moisture, in which case a deposition of hydrated stannic chlorid is liable to occur in the inlet of pipe 46: to prevent clogging from this cause I prefer to provide heating means, as a steam jacket 54,-near the point of entry of the gas. I have observed that even when moist chlorin is passed over the surface of liquid stannic chlorid as herein described, there is no accumulation of hydrated chlorid in the reaction. vessel, but that such hydrated chlorid as is formed is entrained-by the gases and asses therewithto the condensers 49 from w rich it is readily removed. The chlorid formed contains dissolved chlorin and suspended matter or residue, the latter usually consisting in case the original tin-bearing material was a crude metal-bearingpowder such as is obtained by detinning scrap, of tin oXid associated with metallic iron, iron oxid and other impurities. The chlorid and residue are collected. in the still 48. This still is provided with a steam i jacket-.55 having a trapped outlet56. 1 shaft 57, carrying lifting blades or plows 58, is mounted for rotation therein, being driven by any suitable means shown as bevel gears 59. The blades 58 are mounted on the shaft in staggered relation as diagrammatically indicated in Fig. 8, so to effectually lift all portions of the contents in the still. These moving blades are found to greatly expedite the separation of chlorin from the latter, and also the separation of the chlorid from any residue in the still. This portion of iny method is preferably conducted as follows. T he stannic chlorid 51 is an i character.

ment of tin powder from (let-inning operations,

distillation of the which. consists in maintaining a tin-l'mni'ing stainuc in the still, contaming dissolved chlorin and usually a quantity of solid'matter representing the residue of the reaction in vessel 1, heated under conditions of agitation to expel chlorin which is permitted to pass through pipe 60, condenser 51, and thence by pipe 62 to the reaction es sel 1. Thereafter the stannic chlorid is dis tilled, liquefied in condenser 61, and collected in suitable receptacles 63, agitation of the contents of the still bbing u eferably continued, and any uncondensed cilorid being returned to the system through pipe 62. v'hen condensation has substantially ceased, cock 64 in the pipe 65 leading from the still to the conduit 53 may he opened, and air conducted to the still tlfrough pipes 66 in opposite ends of the same. This air is drawn into the still by a suction fan not shown) operatingin connectionwith the scrubber, and is preferably heated, heating means being indicated as torches 67. T heeilect of this admission of air, together with the agitation of the residue, is to accomplish the complete separation of stannic chlorid from the residue.

In case a crude tin-bearing material is treated the dry residue is removed from the still, in which suitable apertures 68 are provided, and is treated in accordance with its A residue derived from the treatand containing in addition to' other substances, metallic iron and tin oxid, is preferably first subjected to treatment, as by mag netic separation of the iron, to concentrate the tin-bearing portions; these portions are thereafter smelted and the metal suitably granulated or subdivided is returned to the reaction vessels for the conversion of the tin into stahnic chlorid. This method of treating the residues is further advantageousba cause it renders it iumecessary to convert all of the metallic tin into stannic chlorid in the vessels 1 at a single operation, any unconverted portions being returned to the vessel with the smelted residue: it will be understood that toward the end of the reaction the combination proceeds less rapidly, and that this methodpf procedure involves a considerable saving of time.

I claim l The method of making stannic chlorid which consists in maintaining a tin-bearing material in suspensionin liquid staunic chlorid, and bringing chlorin into contactwith said. liquid.

2. The method of making sta'nnic chlorid which consists in maintaining a tinbearing material in suspension in liquid stannic chlorid, and passing chlorin in an elongated path over the surface of the liquid.

5. The method. of .u'ialcing staunic chlorid .material in suspension in liquid chlorid, agitating said liquid and bringing; chlorin into contact therewith.

4. The nietlnulv of making stannic chlorid which consists in maintaining atin-bearing material in suspension in liquid stannic chlorid, agitating said liquid, and passing chlorin in an elongated path over the surface of the liquid.

5. The method of making stannic chlorid which consists in circulating a body of liquid stannic chlorid, maintaining tin-bearing material in suspension in one portion thereof, and bringing chlorin into contact with another portion of said. body.

6. The method of making staunio chlorid.

} which consists in providing divided but commumcating bodies of anhydrous stannic chlorid, a t1n-bear1ng material being in contact therewith, establishing a circulation between said bodies, and bringing chlorin into contact therewith.

7. The method of making stannic chlorid. which consists in providing divided but communicating bodies of liquid stannic chlorid, maintaining a tin-bearing material in suspension therein, establishing a circulation between said bodies, and bringing chlorin into contact therewith.

8. The method of making stannic chlorid which consists in circulating a body of liquid stannic chlorid, maintaining a tin-bearing material in suspension in the lower portion thereof, and bringing chlorin into contact with the upper portionof said body.

9. The method of making stannic chlorid which consists in circulating a bodyoi liquid stannic chlorid, maintaining a tin-bearing material in suspension in one-portion thereof, bringing chlorin into contact with another portion, and maintaining the portion in contact with the chlorin at a lowertemperature than the portion in contact with the tin-bean ing material, whereby absorption of the gas is promoted.

10. The method of making stannic chlorid which consists in maintaining a tin-bearing material in suspension in liquid stannic chlorid, bringing chlorin into contact with said liquid, and removing the heat produced by reaction.

11. The method of making stannic chlorid which consists in heating chlorin and causing the same to react on a tln-bearing material n presence of anhydrous stannic chlorid.

12. The method of making stannic chlorid by means of chlorin containing moisture which consists in heating the chlorin to a temperature sufficient to prevent accumula tion of hydrated stannic chlorids, and cansing the heated chlorin to react ona tin-bearing material in presence of anhydrous stannic chlorid.

13. The method of making stannic chlorid which consists in heating a tin-bearing material and reacting :on the same with chlorin in presence of anliydrous stannic chlorid.

14. The method of making chloride of tin which consists in heating a tin-bearing manic chlorid vapors from the reaction Vessel,

and retaining the heat in said vapors leaving said vessel, thereby preventing deposition of crystalline hydrated stannic chlorid in the vapor connections.

17. The methodof making stannic chlorid which consists inreacting with chlorin on a tin-bearing material in presence of a body of anhydrous stannic chlorid, condensing stannic chlorid vap'ors and returning the same'to said body, and continuously removing stan-.

nic chlorid to maintain the volume of th same.

18. The continuous method of making stannic chlorid which consists in supplying a tin-bearing material to a body of liquid stannic chlorid, maintaining it in suspension therein, continuously admitting chlorin drawing the stannic chlorid together with the residue of the reaction. 7 i 19. The method of making stannic chlorid into contact with said liquid, and with-' which consists in maintainin a tin-bearing material in suspension in i uid stannic chlorid, exposing a iilm of said iquid above the surface of the same, and bringing chlorin into contact with said film. I

20. The method of making stannic chlorid which consists in maintaining a tin-bearing material in suspension in liquid stannic chlorid, exposing and constantly renewing a film of said liquid above the surface of the same, and bringing chlorin into contact with said film.

21. The method of making stannic chlorid which consists in agitating a body ofliquid stannic chlorii l, maintaining a tin-bearing material in suspension therein, exposing a iilm of said liquid above the same, and bringing chlorin into contact with said film.

22. The method of making stannic chlorid which consists in agitating a body of liquid stannic chlorid, maintaining a tin-bearing material in suspension therein, exposing films of said liquid above the surface of the same, and directing chlorin in a tortuous path above the surface of the liquid in contact with said films.

surface of the 23. In a method of making stannic chlorid,

the step of'separating stannic chlorid from the residue, which consists in preventing chlorid by heat.

cementing of the residue by agitating the concentrating the tin-bearing portions,

same, and simultaneously expelling the smelting the concentrate and returning the same to the process.

24. In a method of making stannic chlorid, 30. The method of making stannic chlorid the step ofseparating stannic chlorid from which consists in maintaining a tin-bearing the residue, which consists in applyingheat material in suspension in liquid stannic to said residue by a medium out of contact chlorid, bringing chlorid into contact with therewithand simultaneously subjecting the said liquid, purifying the stannic chlorid residue to a current of gas. from chlorin by agitating it and simultane- 25, In a method of makin stannic chlorid, ously ex elling chlorin by heat, then distilthe step of purifyin an "ydrousstannic ling the iquid stannic chlorid and condensing chlorid from disso ve chlorin, which conit, concentrating the tin-bearing portions of sists in agitating the li uid and simultanethe residue, smelting the concentrate, and ously expelling chlorin t erefrom. returning the same to the process.

'26. In amethod of making stannic chlorid, 31. The method of making stannic chlorid the step of purifying stannic chlorid fromwhich consists in maintaining a tin-bearing dissolved chlorin, which consists in agitating material in suspension in liquid stannic the liquid and simultaneously expelling chlorid, bringing-chlorin into contact with chlorin therefrom, and then distilling the said liquid, I pur fying the stannic chlorid residual stannic chlorid and condensing it. from chlorin by ag tating it and simultane- 27. Inamethod of making stannic chlorid, ously expelling chlorin by heat, then dis the step of treating the residues which contilling the liquid stannic chlorid and consists in removing stannic chlorid therefrom, densing it, a itating the residue and expelling concentrating the tin-bearing portions, and the chlorid iy heat, concentrating the tinreturning the concentrate to the process. bearing portions of the'residue, smelting the 28. .In a method of making stannic chlorid, concentrate, and returning the same to the the step of treating the residues which conprocess.

sists in removing stannic chlorid therefrom, In testimony whereof, I affix my signature smelting the remaining portions and returnin presence of two witnesses.

ing the same to the process. ELMER A, SPERRY.

29. In a method of making stannic chlorid, Witnesses:

the step of treating the residues which con- C. W. FOWLER,

sists in removing stannic chlorid therefrom, O. P. TOWNSEND. 

